Synthesis, Characterization, and Oxidation of New POCN<sub>imine</sub>-Type Pincer Complexes of Nickel
作者:Berline Mougang-Soumé、Francine Belanger-Gariépy、Davit Zargarian
DOI:10.1021/om500529e
日期:2014.11.10
(i-Pr-POCNimine-Ph)NiX (X= Br, 6, and NCS, 9) and studied their reactions with various oxidants. Whereas treatment of 6 with Br2 or NBS gave the target 17-electron complex (i-Pr-POCNimine-Ph)Ni(III)Br2 (7), no mixed-ligand trivalent complexes of the type (i-Pr-POCNimine-Ph)Ni(III)Br(X) could be isolated from reactions of (i-Pr-POCNimine-Ph)Ni(NCS) (9) with NBS or of 6 with N-chlorosuccinimide. The latter
该报告描述了二价和三价镍的新型钳型配合物的合成和表征。NiBr 2(CH 3 CN)n和不对称钳型配体Ph-POC H N亚胺-R的回流甲苯混合物以高收率得到(Ph-POCN亚胺-R)Ni(II)Br(Ph-POC H N亚胺-R = 1-(Ph 2 PO),3-(CHNR)C 6 H 4 ; R = Bn,1 ; Ph,2 ; t- Bu,3 ; Cy,4)。NEt 3的存在促进了这些合成过程中的C–H镍化步骤。处理化合物1 - 4被Br 2,我2,Ñ溴代琥珀酰亚胺(NBS)和Ñ氯琥珀酰亚胺的似乎带来期望在这些配合物在Ni(II)中心单电子氧化,但推定的三价物种分解过时间,无法孤立。一个在BR中获得的分解产物的2反应被确定为两性离子化合物[BR 3的Ni(II)κ ø - (ë) - ñ-(3-((二苯基磷酰基)氧基)亚苄基)苯乙铵}],5。为了确定对于稳定三价衍生物的分离重要的因素,我们制备了二价前体(i